Halogenation of aromatic hydrocarbons



Patented Feb. 26, 1946 2,395,777

HALOGENATION OF AROMATIC' HYDROCARBONS 1 Austin S. Brunjes, Plandome', N. Y., and Marcel J. P. Bogart, Teaneck, N. J assignors to The Lummus Company, New York N. Y., a corporation of Delaware Application June 22, 1942, Serial No. 447,983

2 Claims.

This invention relates to an improved method of and apparatus for carrying out the halogenation of an aromatic hydrocarbon and specifically relates to the chlorination of benzene.

With a reaction such as. halogenation of arcmatic hydrocarbons, it is highly desirable to provide optimum temperature control at the zone of reaction, and we also find it desirable to pro- As is well known, chlorinated benzenes are 5 vide for individual unit replacement of apparacommonly used as a base material in the productus. For these reasons the sections I2, 13 and H tion of many chemicals. More particularly, pheare independent, having tube sheets t6 and I8, nol and other products are obtained by the suitl8a and I9, and Na and I1, respectively, to which able conversion of monochlorbenzene. The chlothe reaction tubes 20, 2| and 22 are secured. rination of benzene to produce substantial yields 10 These tubes are in alignment and provide for of monochlorbenzene can not be readily carried the desired flow of reactants as hereinafter deout, however, except by the most careful control scribed. Each tube is filled with a suitable packof the conditions of the reaction, particularly the ing 23, which may consist of any suitable matetemperature, in order to prevent undue side rerial such as ceramic or iron rings. We prefer to actions from taking place. use Raschig rings or the like, and these may be It is one of the principal objects of our inventreated with ferric chloride if desired. tion to provide an improved form-of apparatus A controlled inlet of the reactants (benzene for the chlorination of benzene specifically and and chlorine) to these tubes can be accomplished for the carrying out of similar reactions in genmost successfully according to our invention by eral, in which apparatus intimate mixing of the injecting the benzene through a chamber of reactants and accurate temperature control of chlorine. This may be accomplished by introthe reaction are accomplished. ducing the chlorine as a gas into chamber llb A further object of our invention is to provide through inlets 2.6 and forcing the benzene as a an improved process for specifically controlling liquid into chamber Ila through inlet and the reaction 7 between chlorine and benzene 25 thence through distributor plate 28. whereby the maximum yield of monochlorben- This plate 28 contains a plurality of' nozzles zene and the minimum yield of polychlorbenzenes 29 in alignment with the lower ends of the reacare obtained, or alternatively, the production of tion tubes 20, which are desirably V-notched as a maximum yield of polychlorbenzenes. at Ma. This assures the introduction of the mix- Astill further object of our invention is to pro- 30 ture of benzene and chlorine into these tubes vide an improved continuous process for halothrough the jet action of the nozzles 29. It is to genating aromatic hydrocarbons such as benbe noted that the chlorine inlets 26 are positioned zene to produce desired halogenated hydrocarabove the lower end of the tubes 20 so that the bons such as chlorbenzene useful in the producchlorine is drawn into the reaction tubes by tion of industrial materials, which process is parmeans of the jet action. ticularly adapted for large-scale, economical op- The reaction sections l2, l3 and H are prefereration and simplified control. ably so arranged within the reaction vessel Ill Further objects and advantages of our inventhat a suitable cooling medium can be independtion will appear from the following description ently circulated about them in indirect heat exof a preferred form of embodiment thereof taken 40 change therewith. This is most important when in connection with the attached drawing, in the reaction is exothermic and it is necessary to which the figure is a vertical section through our regulate the temperature of the reaction to preimproved reaction chamber, with which the'revent side reactions from taking place. This is lated apparatus is shown in schematic flow diathe case in the formation of chlorbenzenes, the gram. formation of monochlorbenzene being best ac- As a specific form of embodiment of our invencomplished at temperatures of 40 to 45 C. wheretion, we prefer to build the reaction vessel ill in as formation of polychlorbenzenes is best accoma series of sections. The lowest section II is a plished at around '75 to 85 C. For this reason, feed chamber and may have a neutralizing chamit is necessary to precisely control the cooling efber. This section also acts as the foundation for 5 feet in the respective sections. the entire vessel. It is surmounted by several We have found that water is a satisfactory coolshell and tube heat exchange and reaction secing medium. Cooling water inlet nozzles 30, 30a, tions, of which three, l2, l3 and I, are shown. and 30b, respectively, may be interconnected The uppermost section l5 may be termed the with inlet manifold 32 and cooling water disvapor chamber section. charge nozzles 3|, 3la, and Slb, respectively,

may be interconnected to the discharge manifold 33. It desired, the cooling water may pass through the upper two sections l3 and H in series and cross-connection 34 may be used for this purpose. Suitable valves will be provided for regulating the flow of cooling water.

It will generally be necessary to remove the largest amount of heat in the-lowermost heat exchange-reaction section l2, and a close temperature control in this section is necessary. For this purpose valve 35 can be interconnected with a. suitable temperature controller generally indicated at 38 so that the flow of cooling water through inlet nozzle 30 may be automatically controlled by the exit temperature of reaction section 12. It is to be noted that the several heat exchange-reaction sections are desirably provided with bellies 38 for the suitable dis- I tribution of the cooling water about the reaction tubes. 1

Benzene and chlorine reactants as previously indicated pass upwardly through the reaction tubes and come into contact with the packing therein. This packing provides for a substantially complete mixing of these reactants and also insures that the reactants come into intimate contact with each other. The reaction takes place for the most part in the lower portion of the reacting tubes, although the reacting tubes are suihciently long so that the reaction is substantially complete by the time thereactants have traversed the length of these tubes. The ends of these tubes are also V-notched at the top, which facilitates the separation of the gases from the liquid products at the upper part of the reaction zone.

Apparatus may be used for counterflow chlorination by introducing benzene at top and chlorine at bottom when it is desirable to do so.

The mixture of reaction products discharged from the reaction tubes is partially in the liquid and partially in the vapor state. This reaction mixture consists of chlorbenzenes, unreacted benzene, and hydrogen chloride. The liquid portion the reaction mixture is removed through nozzle 39. The vapor portion of the reaction mixture is removed from reaction vessel through nozzle 40 and is passed through line 4| to condenser 42 wherein the vaporized benzene and chlorbenzene are condensed. A suitable cooling medium may be circulated through condenser 42 by means of lines. The condensed material is separated from the uncondensed hydrogen chloride in separator 44, from which the condensate is returned through line 45 to the vapor chamber section ii. The uncondensed hydrogen chloride: will the removed in its gaseous state through line 41 to a suitable recovery system or the like. It is to be noted that the condensate is reintroduced into section I5 through nozzle 48, whichv is so designed that its discharge is below the upper end of the reacting tubes 22. Thus nozzle 48 discharges the condensate below the level of liquid in section l5, which aids in the recovery of the liquid product.

The liquid portion of the reaction mixture removed through nozzle 39 is passed through line 50 into heater 5| wherein a portion of this liquid is heated to the boiling point to remove as much hydrogen chloride as possible. A suitable heating material such as steam may be circulated through heater Bl as by means of lines 52 and 52a tor this purpose. .The partially vaporized liquid is passed through line 54 into the flash chamber 55 wherein the vaporized portion of the liquid is separated from the unvaporized portion. This vaporized portion comprises the hydrogen chloride dissolved in the liquid together with some benzene and chlorbenzene vapors. The vapors are passed through line 56 for admixture with the vapors in line 4|. Any liquid contained therein will drop back to the chamber IS with thevapor portion continuing to the condensed 42.

The liquid in flash chamber 55 is removed therefrom through line 58 and may be withdrawn as product at 68a or be introduced through nozzle 59 into the neutralizing chamber 80 formed by the dished head SI and the bottom of the section II. This liquid comprises benzene and chlorbenzene containing a very small percentage of dissolved hydrogen chloride and, if a neutral product is desired,it may be neutralized by adding a. neutralizing agent such as caustic soda. This is suitably introduced into the neutralizing chamber through nozzle 62. An a itator 63 driven by motor 64 is provided-to effect a mixing of caustic with the benzene and chlorbenzene. The neutralized product is discharged from chamber through nozzle 66 and may be passed to a suitable settler (not shown) in which the sludge of caustic and sodium chloride is settled out and separated from the benzene and chlorbenzene.

We have found it preferable to fabricate reaction vessel It) as an integrated unit as shown. In this manner not only is a compact vessel provided, but the amount of space necessary, for the equipment is materially reduced. As indicated, the bottom of the feed chamber section Il may be provided with a suitable drain 68. The neutralizing chamber may also be provided with a suitable drain 69 as well as a vent 10 for the removal of any uncondensable material. Ordinarily we find it desirable to operate the reaction section under a slight superatmospheric pressure.

The apparatus is particularly adapted for the maximum production of monochlorbenzene and in such case appropriate temperatures are ob- 5 tained by the use of controlled flow of the cooling liquid. However, if it is desired to produce a maximum yield of polychlorbenzenes, higher temperatures are desirable, and it may be found desirable to introduce steam in the heat exchange 50 sections rather than water.

The apparatus is also adapted to further chlorinate partially chlorinated aromatic hydrocarbons or other organic liquids by changing the type of feed. It may also be found desirable to 55 introduce additional amounts of either chlorine or benzene or both at intermediate points along the length of the reaction tubes by introducing either or both materials into the compartments between the respective tube sheets 18 and Ila no and I9 and Na. Such operation may be found desirable to better control the reaction.

Although we have shown and described'a preferred form of embodiment of our invention, it will be understood that modifications may be made thereto; therefore, only such limitations as appear in the claims appendedhereinaiter should be made.

We claim:

1. Apparatus for conducting a reaction ber 70 tween a liquid and a gas. comprising an elongated vertically extending shell, vertically spaced transverse partitions dividing said shell into a plurality of superposed chambers, the lowermost one of said chambers forming a first feed chamber ior'a 76 liquid reactant,'the chamber immediately above it forming a second feed chamber fora gaseous reactant, and the remaining chambers comprising a series of alternate relatively deep and shallow, chambers, and a discharge chamber above said series, vertically extending transversely spaced tubes within each of said deep chambers and fixed in the partitions forming the upper and lower sides of the chamber, the tubes of adjacent deep sections opening into'the shallow chambers therebetween, the tubes of the uppermost deep chamber opening into the said discharge chamber, and the tubes of the lowermost deep chamber opening into the upper one of said feed chambers to receive the gaseous reactant, and nozzles in vertical alignment with the tubes opening into said gas feed chamber and extending upwardly from the lower feed chamber to discharge the liquid reactant therefrom and. into said tubes, each deep chamber having an inlet and an outlet for a heat exchange fluid.

2. Apparatus for conducting a reaction, comprising an elongated vertically extending shell, vertically spaced transverse partitions dividing said shell into a plurality of superposed chambers, the lowermost one of said chambers forming a first feed chamber for a fluid reactant, the chamber immediately above it forming a second feed chamber for another fluid reactant, and the remaining chambers comprising a series of alternate relatively deep and shallow chambers, and a discharge chamber above said series, vertically extending transversely spaced tubes within each of said deep chambers and fixed in the partitions forming the upper and lower sides of the chamber, the tubes of adjacent deep sections opening into the shallow chambers therebetween, the tubes of theuppermost deep chamber opening into the said discharge chamber, and the tubes of the lowermost deep chamber opening into the upper one of said feed chambers to receive the reactant therefrom, nozzles in vertical alignment with the tubes opening into said upper feed chamber and extending upwardly from the lower feed chamber to discharge the other reactant therefrom and into said tubes, each deep chamber having an inlet and an outlet for a heat exchange fluid, and means responsive to varia' tions in temperature within the lowermost one oi said shallow chambers to control circulation of the heat exchange fluid through the lowermost one of said deep chambers.

AUSTIN S. BRUNJES.

MARCEL J. P. BOGART. 

